Silicon-containing layer deposition with silicon compounds

ABSTRACT

Methods for depositing a silicon-containing film are described. The methods may include delivering a silicon compound to a surface or a substrate, and reacting the silicon compound to grow the silicon-containing film. The silicon compound may be one or more compounds having a formula selected from the group Si 4 X 8 , Si 4 X 10 , Si 5 X 10 , and Si 5 X 12 , where X is independently a hydrogen or halogen.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 10/688,797, filedOct. 17, 2003 now U.S. Pat. No. 7,540,920, which claims benefit of U.S.Ser. No. 60/419,376, filed Oct. 18, 2002, U.S. Ser. No. 60/419,426,filed Oct. 18, 2002, and U.S. Ser. No. 60/419,504, filed Oct. 18, 2002,which are herein incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to deposition ofsilicon-containing films, and more particularly to silicon compoundcompositions and related processes to deposit silicon-containing films.

2. Description of the Related Art

Atomic layer epitaxy (ALE) offers meticulous control of film thicknessby growing single atomic layers upon a crystal lattice. ALE is employedto develop many group IV semiconductor materials, such as silicon,germanium, silicon germanium, silicon carbon and silicon germaniumcarbon. Silicon based materials, produced via ALE, are of interest foruse as semiconductor materials. The silicon based materials can includegermanium and/or carbon at selectable concentrations and are grown aspolysilicon, amorphous or monocrystalline films. Silicon-ALE, in which asilicon-containing film is epitaxial grown, consists of two steps.

A monolayer of partially decomposed source gas molecules (e.g., SiH4 orSiH2Cl2) is adsorbed over the substrate or surface. The adsorbate mayconsists of a silicon atom and at least another kind of atom or groupbonded with silicon, such as chlorine, hydrogen or methyl (e.g., SiCln,SiHn or H4-nSiMen, where n=1-4). The adsorbate decomposes to formadatoms of silicon on the surface. The adatoms migrate or diffuse on thesurface to an empty lattice site of the silicon crystal. The crystalcontinues to form and grow as adatoms are generated on the crystallinesurface and incorporated into the lattice. By-product removal isachieved and a new surface is created on the monolayer. The monolayergrowth in the next cycle is made possible.

Source gases used during silicon deposition include lower silanes (e.g.,silane, dichlorosilane and tetrachlorosilane) as well as higher silanes(e.g., disilane, hexachlorodisilane and trisilane). Silane anddichlorosilane are the most common source gases used during Si-ALE, suchas described in U.S. Ser. No. 09/963,411, published as U.S. Pub. No.2002-0052077, and issued as U.S. Pat. No. 6,384,437. These lower silanesrequire the substrate to be maintained at high temperatures, often inthe range of 800-1,000° C. Higher silanes are utilized as source gasesto lower the temperature needed during Si-ALE. Disilane is used to growsilicon by ultraviolet-photostimulated ALE in the temperature range of180-400° C., as demonstrated by Suda, et al., J. Vac. Sci. Technol. A, 8(1990) 61, as well as by Lubben, et al., J. Vac. Sci. Technol. A, 9(1991) 3003. Furthermore, trisilane is used as a source gas duringSi-ALE at about 380° C., as reported by Imai, et al., Jpn. J. Appl.Phys., 30 (1991) 3646.

Si-ALE with supplemental etchants has also been realized. Horita, etal., U.S. Ser. No. 09/991,959, published as U.S. Pub. No. 2002-0127841,and issued as U.S. Pat. No. 6,503,799, teaches the combination ofdichlorosilane and hydrogen chloride to accomplish selective silicongrowth. Supplemental etchants are generally halogenated and/or radicalcompounds (e.g., HCl or .Cl) that necessitate high reactivity.Therefore, hazardous and toxic conditions are often associated withetchant use.

Therefore, there is a need to provide silicon-containing compounds thatprovide both a source chemical for silicon deposition and a sourcechemical as an etchant. The silicon-containing compounds should beversatile to be applied in a variety of silicon depos

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the invention generally provides a method fordepositing a silicon-containing film, comprising delivering a siliconcompound to a substrate surface and reacting the silicon compound todeposit the silicon-containing film on the substrate surface. Thesilicon compound comprises a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₆ comprise at least one hydrogen and atleast one halogen.

In another embodiment, the invention generally provides a composition ofmatter comprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₆ comprise at least one hydrogen and atleast one halogen and the proviso that R is not carbon when X₄, X₅ andX₆ are fluorine.

In another embodiment, the invention generally provides a composition ofmatter comprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen and R is germanium.

In another embodiment, the invention generally provides a method fordepositing a silicon-containing film, comprising delivering a siliconcompound to a substrate surface and reacting the silicon compound todeposit the silicon-containing film on the substrate surface. Thesilicon compound comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₈ comprise at least one halogen.

In another embodiment, the invention generally provides a composition ofmatter comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₈ comprise at least one halogen.

In another embodiment, the invention generally provides a composition ofmatter comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen and R is germanium.

In another embodiment, the invention generally provides a method fordepositing a silicon-containing film by delivering a silicon compound toa substrate surface and reacting the silicon compound to deposit thesilicon-containing film on the substrate surface. In some embodiments,the silicon compound comprises three silicon atoms, fourth atom ofcarbon, silicon or germanium and atoms of hydrogen or halogen with atleast one halogen. In other embodiments, the silicon compound comprisesfour silicon atoms, fifth atom of carbon, silicon or germanium and atomsof hydrogen or halogen with at least one halogen. In some embodiments,the silicon-containing film is selected from the group consisting ofsilicon, silicon germanium, silicon carbon and silicon germanium carbon.

In another embodiment, the invention generally provides a composition ofmatter comprising three silicon atoms, fourth atom of carbon, silicon orgermanium and atoms of hydrogen or halogen with at least one halogen. Inother embodiments, the invention generally provides a composition ofmatter comprising four silicon atoms, fifth atom of carbon, silicon orgermanium and atoms of hydrogen and/or halogen.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the invention pertain to processes for epitaxiallydepositing silicon-containing films of a desired thickness on asubstrate. The processes generally include silicon compounds thatcontain silicon sources, as well as etchant sources, within the samemolecule. A silicon source is a compound that includes from at least onesilicon atom and to five silicon atoms. An etchant source is a compoundthat includes at least one functional group with etchantcharacteristics. In some embodiments, molecules are used that alsocontain silicon germanium sources or silicon carbon sources.

In one aspect, embodiments of the invention relate to silicon compoundscomprising a structure:

wherein X₁-X₆ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₆ comprise at least one hydrogen and atleast one halogen.

Silicon sources have formulas such as Cl₃SiSiCl₂H, Cl₃SiSiClH₂,Cl₃SiSiH₃, HCl₂SiSiH₃, H₂ClSiSiH₃, HCl₂SiSiCl₂H and H₂ClSiSiClH₂. Othersilicon sources are derived by the replacement of at least one H-atomand/or at least one Cl-atom with another halogen, such as fluorine.Therefore, silicon sources may have chemical formulas such asCl₃SiSiF₂H, F₃SiSiClH₂, F₃SiSiH₃, F₃SiSiCl₃, HFClSiSiF₃, H₂ClSiSiH₃,FCl₂SiSiF₂H and H₂ClSiSiClF₂. Other similarly halogenated siliconsources enable the processes.

Silicon germanium sources may have formulas such as Cl₃SiGeCl₃,H₃SiGeH₃, Cl₃SiGeCl₂H, Cl₃SiGeClH₂, Cl₃SiGeH₃, HCl₂SiGeH₃, H₂ClSiGeH₃,HCl₂SiGeCl₂H, H₂ClSiGeClH₂, Cl₃GeSiCl₂H, Cl₃GeSiClH₂, Cl₃GeSiH₃,HCl₂GeSiH₃, H₂ClGeSiH₃, HCl₂GeSiCl₂H and H₂ClGeSiClH₂. Other silicongermanium sources are derived by the replacement of at least one H-atomand/or at least one Cl-atom with another halogen, such as fluorine.Therefore, silicon germanium sources may have chemical formulas such asF₃SiGeCl₃, F₃SiGeH₃, F₃GeSi₃, F₃GeSiH₃, H₃SiGeCl₃, H₃SiGeHCl₂,F₃SiGeCl₂H, F₃SiGeClH₂, HCl₂SiGeH₃, H₂ClSiGeF₃, FCl₂SiGeCl₂H,H₂ClSiGeClH₂, F₃GeSiCl₂H, F₃GeSiClH₂ and H₂FGeSiClH₂. Other similarlyhalogenated silicon germanium sources enable the processes.

Silicon carbon sources may have formulas such as H₃SiCH₃, Cl₃SiCCl₃,Cl₃SiCCl₂H, Cl₃SiCClH₂, Cl₃SiCH₃, HCl₂SiCH₃, H₂ClSiCH₃, HCl₂SiCCl₂H,H₂ClSiCClH₂, Cl₃CSiCl₂H, Cl₃CSiClH₂, Cl₃CSiH₃, HCl₂CSiH₃, H₂ClCSiH₃,HCl₂CSiCl₂H and H₂CiCSiClH₂. Other silicon carbon sources are derived bythe replacement of at least one H-atom and/or at least one Cl-atom withanother halogen, such as fluorine. Therefore, silicon carbon sources mayhave chemical formulas such as Cl₃SiCF₂H, Cl₃SiCFH₂, F₃SiCH₃, FCl₂SiCH₃,H₂FSiCH₃, FCl₂SiCCl₂H, FH₂ClSiCClH₂, FCl₃CSiCl₂H, Cl₃CSiClHF, F₃CSiH₃,F₃CSiCl₃, H₃CSiF₃, Cl₃CSiF₃, FCl₂CSiH₃, H₂FCSiH₃, FCl₂CSiCl₂H andH₂ClCSiFH₂. Other similarly halogenated silicon carbon sources enablethe processes.

Silicon compounds may be used to deposit a silicon motif (e.g., Si—R,where R is silicon, germanium or carbon) contained within the molecule.The hydrogens and/or halogens are ligands that are removed from themolecule as the silicon motif is reduced and deposited. The depositionforms a silicon-containing film during the procedure. The ligands mayform an in-situ etchant from the liberated hydrogen and/or halogen. Thein-situ etchants include H, H₂, HX, X, X₂ and XX′, where X and X′ aredifferent, but both halogen, as well as other combinations of hydrogenand halogen molecules including radical or ionic species (e.g., .H or.X). Herein, the word halogen includes fluorine, chlorine, bromine,iodine, radicals thereof, ions thereof and combinations thereof.

In another aspect, embodiments of the invention relate to siliconcompound comprising structures:

wherein X₁-X₈ are independently hydrogen or halogen, R is carbon,silicon or germanium and X₁-X₈ comprise at least one halogen. In someembodiments, the silicon-containing film is selected from the groupconsisting of silicon, silicon germanium, silicon carbon and silicongermanium carbon.

Other silicon compounds are used to deposit a silicon motif (e.g.,Si—Si—R or Si—R—Si, where R is silicon, germanium or carbon) containedwithin the molecule. Silicon sources may have formulas such asH₃SiSiH₂SiH₂Cl, H₃SiSiH₂SiHCl₂, H₃SiSiH₂SiCl₃, H₃SiSiHClSiH₂Cl,H₃SiSiHClSiHCl₂, H₃SiSiHClSiCl₃, H₃SiSiCl₂SiH₂Cl, H₃SiSiCl₂SiHCl₂,H₃SiSiCl₂SiCl₃, HCl₂SiSiH₂SiH₂Cl, HCl₂SiSiH₂SiHCl₂, Cl₃SiSiH₂SiCl₃,HCl₂SiSiCl₂SiH₂Cl, H₂ClSiSiHClSiHCl₂, Cl₃SiSiH₂SiCl₃, Cl₃SiSiHClSiCl₃,HCl₂SiSiCl₂SiHCl₂ and H₃SiSiCl₂SiH₃. Other silicon sources are derivedby the replacement of at least one H-atom and/or at least one Cl-atomwith another halogen, such as fluorine. Therefore, silicon sources mayhave formulas such as F₃SiSiH₂SiH₃, F₃SiSiH₂SiCl₃, H₃SiSiH₂SiH₂F,H₃SiSiH₂SiHF₂, H₃SiSiH₂SiF₃, H₃SiSiHFSiH₂Cl, F₃SiSiHClSiHF₂,H₃SiSiFHSiCl₃, H₃SiSiF₂SiH₂F, H₃SiSiCl₂SiFCl₂ and H₃SiSiF₂SiCl₃. Othersimilarly halogenated silicon sources enable the processes. Furthermore,cyclic-trisilane and cyclic-halotrisilane are used within the scope ofthe invention.

Silicon germanium sources may have formulas such as H₃SiSiH₂GeH₂Cl,H₃SiSiH₂GeH₃, H₃SiSiH₂GeHCl₂, H₃SiSiH₂GeCl₃, H₃SiSiHClGeH₂Cl,H₃SiSiHClGeHCl₂, H₃SiGeHClSiCl₃, H₃SiGeCl₂SiH₂Cl, H₃SiGeCl₂SiHCl₂,H₃SiGeCl₂SiCl₃, HCl₂SiGeH₂SiH₂Cl, HCl₂SiSiH₂GeHCl₂, Cl₃SiSiH₂GeCl₃,HCl₂SiGeCl₂SiH₂Cl, H₂ClSiGeHClSiHCl₂, Cl₃SiGeH₂SiCl₃, Cl₃SiSiHClGeCl₃,HCl₂SiGeCl₂SiH₃ and H₃GeSiCl₂SiH₃. Other silicon germanium sources arederived by the replacement of at least one H-atom and/or at least oneCl-atom with another halogen, such as fluorine. Therefore, silicongermanium sources have formulas such as F₃SiSiH₂GeH₃, F₃SiSiH₂GeCl₃,F₃GeSiH₂SiH₃, F₃GeSiH₂SiCl₃, F₃SiGeH₂SiH₃, F₃SiGeH₂SiCl₃,F₃SiSiH₂GeCl₂H, H₃SiSiF₂GeH₂Cl, F₃SiSiH₂GeHCl₂, H₃SiSiF₂GeCl₃,H₃SiSiCl₂GeH₂Cl, H₃SiSiHClGeHF₂, H₃SiGeH₂SiCl₃, H₃SiGeCl₂SiH₂Cl,F₃SiGeCl₂SiHCl₂, H₃SiGeF₂SiCl₃. Other similarly halogenated silicongermanium sources enable the processes. Furthermore, cyclicgermaniumsilanes and cyclic-halogermaniumsilanes are used within thescope of the invention.

Silicon carbon sources may have formulas such as H₃SiSiH₂CH₂Cl,H₃SiSiH₂CHCl₂, H₃SiSiH₂CCl₃, H₃SiSiHClCH₂Cl, H₃SiSiHClCHCl₂,H₃SiCHClSiCl₃, H₃SiCCl₂SiH₂Cl, H₃SiCCl₂SiHCl₂, H₃SiCCl₂SiCl₃,HCl₂SiCH₂SiH₂Cl, HCl₂SiSiH₂CHCl₂, Cl₃SiSiH₂CCl₃, HCl₂SiCCl₂SiH₂Cl,H₂ClSiCHClSiHCl₂, Cl₃SiCH₂SiCl₃, Cl₃SiSiHClCCl₃, HCl₂SiCCl₂SiH₃ andH₃CSiCl₂SiH₃. Other silicon carbon sources are derived by thereplacement of at least one H-atom and/or at least one Cl-atom withanother halogen, such as fluorine. Therefore, silicon carbon sourceshave formulas such as F₃SiSiH₂CH₃, F₃SiSiH₂CCl₃, F₃CSiH₂SiH₃,F₃CSiH₂SiCl₃, F₃SiCH₂SiH₃, F₃SiCH₂SiCl₃, F₃SiSiH₂CCl₂H, H₃SiSiF₂CH₂Cl,F₃SiSiH₂CHCl₂, H₃SiSiF₂CCl₃, H₃SiSiHFCH₂Cl, H₃SiSiHClCHF₂, H₃SiCHFSiCl₃,H₃SiCCl₂SiH₂F, F₃SiCCl₂SiHCl₂, H₃SiCF₂SiCl₃. Other similarly halogenatedsilicon carbon sources enable the processes. Furthermore,cyclic-carbosilanes and cyclic-halocarbosilanes are used within thescope of the invention.

In another aspect, embodiments of the invention relate to siliconcompounds, compounds 1-8, having the following representativestructures:

where X₁-X₁₀ are independently hydrogen or halogen, such as fluorine,chlorine, bromine or iodine and R is carbon, silicon or germanium.

In another aspect, embodiments of the invention relate to siliconcompounds, compounds 9-32, having the following representativestructures:

where X₁-X₁₂ are independently hydrogen or halogen, such as fluorine,chlorine, bromine or iodine and R is carbon, silicon or germanium. Thestructures of compounds 1-32 are representative and do not imply aparticular isomer. Herein, any elemental name or chemical symbolanticipates the use of the respective elemental isotopes, such as theuse of hydrogen (¹H or H) also includes the use of deuterium (²H or D)and tritium (³H or T).

Therefore, silicon compounds may be used to deposit a silicon motif(e.g., Si₃R or Si₄R, where R is silicon, germanium or carbon) containedwithin the molecule. The silicon motif of compounds 1-8 is representedby Si₃R and the silicon motif of compounds 9-32 is represented by Si₄R.The hydrogens and/or halogens are ligands that are removed from themolecule as the silicon motif is reduced and deposited. The depositionforms a silicon-containing film during the deposition process.

Silicon sources may include compounds with the formulas Si₄X₈, Si₄X₁₀,Si₅X₁₀ and Si₅X₁₂, where X is independently hydrogen or halogen. Siliconsources containing hydrogen and/or chlorine may include compounds withthe formulas Si₄H_(8−n)Cl_(n), Si₄H_(10−m)Cl_(m), Si₅H_(10−p)Cl_(p) andSi₅H_(12−q)Cl_(q), where n=1-8, m=1-10, p=1-10 and q=1-12. Siliconsources may include Si₄H₉Cl, Si₄H₈Cl₂, Si₄H₇Cl₃, Si₄H₆Cl₄, Si₄H₅Cl₅,Si₄H₄Cl₆, Si₄H₃Cl₇, Si₄H₂Cl₈, Si₄HCl₉, Si₄Cl₁₀, Si₅H₁₁Cl, Si₅H₁₀Cl₂,Si₅H₉Cl₃, Si₅H₈Cl₄, Si₅H₇Cl₅, Si₅H₆Cl₆, Si₅H₅Cl₇, Si₅H₄Cl₈, Si₅H₃Cl₉,Si₅H₂Cl₁₀, Si₅HCl₁₁ and Si₅Cl₁₂. Other silicon sources are derived bythe replacement of at least one Cl-atom with another halogen, such asfluorine, bromine or iodine and enable the processes. In one example,isotetrasilane, (SiH₃)₃SiH, is a silicon source compound. In anotherexample, neopentasilane, (SiH₃)₄Si, is a silicon source compound.Furthermore, cyclic-tetrasilane, cyclic-halotetrasilane,cyclic-pentasilane and cyclic-halopentasilane are used within the scopeof the invention.

Silicon germanium sources may include compounds with the formulasSi₃GeX₈, Si₃GeX₁₀, Si₄GeX₁₀ and Si₄GeX₁₂, where X is independentlyhydrogen or halogen. Silicon germanium sources containing hydrogenand/or chlorine may include compounds with the formulasSi₃GeH_(8−n)Cl_(n), Si₃GeH_(10−m)Cl_(m), Si₄GeH_(10−p)Cl_(p) andSi₄GeH_(12−q)Cl_(q), where n=1-8, m=1-10, p=1-10 and q=1-12. Silicongermanium sources may include Si₃GeH₉Cl, Si₃GeH₈Cl₂, Si₃GeH₇Cl₃,Si₃GeH₆Cl₄, Si₃GeH₅Cl₅, Si₃GeH₄Cl₆, Si₃GeH₃Cl₇, Si₃GeH₂Cl₈, Si₃GeHCl₉,Si₃GeCl₁₀, Si₄GeH₁₁Cl, Si₄GeH₁₀Cl₂, Si₄GeH₉Cl₃, Si₄GeH₈Cl₄, Si₄GeH₇Cl₅,Si₄GeH₆Cl₆, Si₄GeH₅Cl₇, Si₄GeH₄Cl₈, Si₄GeH₃Cl₉, Si₄GeH₂Cl₁₀, Si₄GeHCl₁₁and Si₄GeCl₁₂. Other silicon germanium sources are derived by thereplacement of at least one Cl-atom with another halogen, such asfluorine, bromine or iodine and enable the processes. Furthermore,cyclic germaniumsilanes and cyclic-halogermaniumsilanes are used withinthe scope of the invention.

Silicon carbon sources may include compounds with the formulas Si₃CX₈,Si₃CX₁₀, Si₄CX₁₀ and Si₄CX₁₂, where X is independently hydrogen orhalogen. Silicon carbon sources containing hydrogen and/or chlorine mayinclude compounds with the formulas Si₃CH_(8−n)Cl_(n),Si₃CH_(10−m)Cl_(m), Si₄CH_(10−p)Cl_(p) and Si₄CH_(12−q)Cl_(q), wheren=1-8, m=1-10, p=1-10 and q=1-12. Silicon carbon sources may includeSi₃CH₉Cl, Si₃CH₈Cl₂, Si₃CH₇Cl₃, Si₃CH₆Cl₄, Si₃CH₅Cl₅, Si₃CH₄Cl₆,Si₃CH₃Cl₇, Si₃CH₂Cl₈, Si₃CHCl₉, Si₃CCl₁₀, Si₄CH₁₁Cl, Si₄CH₁₀Cl₂,Si₄CH₉Cl₃, Si₄CH₈Cl₄, Si₄CH₇Cl₅, Si₄CH₆Cl₆, Si₄CH₅Cl₇, Si₄CH₄Cl₈,Si₄CH₃Cl₉, Si₄CH₂Cl₁₀, Si₄CHCl₁₁ and Si₄CCl₁₂. Other silicon carbonsources are derived by the replacement of at least one Cl-atom withanother halogen, such as fluorine, bromine or iodine and enable theprocesses. Furthermore, cyclic carbonsilanes andcyclic-halocarbonsilanes are used within the scope of the invention.

Many of the silicon compounds are in the gaseous or liquid state atambient pressure and temperature. However, during a deposition process,the silicon compounds may be in solid, liquid, gas or plasma state ofmatter, as well as radical or ionic. In general, the silicon compoundsmay be delivered to the substrate surface by a carrier gas. Carrier orpurge gases may include N₂, H₂, Ar, He, forming gas and combinationsthereof.

Silicon compounds may be used solely or in combination with compounds,including other silicon compounds, to deposit silicon-containing filmswith a variety of compositions. In one example, a silicon compound, suchas Cl₃SiSiH₂SiH₂SiH₃, is used to etch the substrate surface, as well asto epitaxially grow a crystalline silicon film on the substrate. Inanother example, the substrate surface may need a different etchant thanin the previous example. Therefore, Cl₃SiSiH₂SiCl₂SiH₂F is used in theetching process, while H₂ClSiSiH₂SiH₂SiH₃ is used in the depositionprocess. In another example, a silicon germanium source, such asH₃SiSiH₂SiH₂GeHCl₂, is used to continue the deposition process and togrow a silicon germanium film on the silicon film.

In another embodiment, the RF₃ fragment, where R═Si, Ge or C, can beincorporated into the molecule. The RF₃ is thermodynamically stable dueto the strong R—F bond. A molecule, such as F₃CSiH₂SiH₃SiH₃, decomposesto deposit silicon-containing films, while the CF₃ fragment is generatedas part of a volatile product. A silicon compound with the RF₃ fragmentcan have favorable properties, such as volatility (vapor pressure andboiling point).

Silicon compounds are utilized within embodiments of the processes todeposit silicon-containing films used for Bipolar (base, emitter,collector, emitter contact), BiCMOS (base, emitter, collector, emittercontact) and CMOS (channel, source/drain, source/drain extension,elevated source/drain, substrate, strained silicon, silicon oninsulator, isolation, contact plug). Other embodiments of processesteach the growth of silicon-containing films that can be used as gate,base contact, collector contact, emitter contact, elevated source/drainand other uses.

Embodiments of the invention teach processes to grow selective siliconfilms or blanket silicon films. Selective silicon film growth generallyis conducted when the substrate or surface includes more than onematerial, such as a crystalline silicon surface having oxide or nitridefeatures. Usually, these features are dielectric material. Selectiveepitaxial growth to the crystalline, silicon surface is achieved whilethe feature is left bare, generally, with the utilization of an etchant(e.g., HCl). The etchant removes amorphous silicon or polysilicon growthfrom features quicker than the etchant removes crystalline silicongrowth from the substrate, thus selective epitaxial growth is achieved.In some embodiments, selective epitaxial growth of thesilicon-containing film is accomplished with the use of no etchants.During blanket silicon epitaxy, a film grows across the whole substrateregardless of particular surface features and compositions.

Embodiments of the invention teach processes to grow selective siliconfilms or blanket silicon films. Selective silicon film growth generallyis conducted when the substrate or surface includes more than onematerial, such as a crystalline silicon surface having oxide or nitridefeatures. Usually, these features are dielectric material. Selectiveepitaxial growth to the crystalline, silicon surface is achieved whilethe feature is left bare, generally, with the utilization of an etchant(e.g., HCl). The etchant removes amorphous silicon or polysilicon growthfrom features quicker than the etchant removes crystalline silicongrowth from the substrate, thus selective epitaxial growth is achieved.In some embodiments, selective epitaxial growth of thesilicon-containing film is accomplished with the use of no etchants.During blanket silicon epitaxy, a film grows across the whole substrateregardless of particular surface features and compositions.

Embodiments of the invention may use processes with an etchant sourceand a silicon source incorporated into the silicon compound. Thedeposition processes form silicon-containing films and liberate ligandsfrom the silicon compounds. The ligands, hydrogen and/or halogen, arein-situ etchants. The in-situ etchants include H, H₂, HX, X, X₂ and XX′,where X is a halogen and X′ is a different halogen than X, as well asany other combinations of hydrogen and halogen molecules includingradical or ionic species. However, supplemental etchants can also beused with the silicon compounds and are demonstrated in variousembodiments of the invention. Supplemental etchants can include: CHF₃,CF₄, C₄F₈, CH₂F₂, ClF₃, Cl₂, F₂, Br₂, NF₃, HCl, HF, HBr, XeF₂, NH₄F,(NH₄)(HF₂) and SF₆. For example, H₃SiSiH₂SiH₂SiCl₂H and HCl are usedduring the growth of a silicon-containing film.

In some processes, silicon compounds are introduced to the heated (e.g.,500° C.) surface of a substrate and the silicon motif is deposited asthe silicon-containing film. The liberated ligands of the siliconcompounds are converted to an in-situ etchant. The in-situ etchantssupport in the growth of selective silicon epitaxy by removing amorphoussilicon or polysilicon from substrate features (e.g., oxides ornitrides) at a faster rate than removing crystalline silicon from thesurface. Hence, crystalline silicon grows about the substrate features.

Reducing agents may be used in various embodiments of the invention totransfer electrons between compounds. Generally, silicon compounds arereduced to elemental films during deposition, while the ligands (e.g.,hydrogen or halogen) are detached from the silicon motif. Reducingagents may include: mono- and diatomic hydrogen, borane, diborane,alkyboranes (e.g., Me₃B or Et₃B), metals and organometallic compoundsamong others. In one example, a silicon-containing film is deposited byalternating pulses of F₃SiSiH₂SiH₂CH₃ with atomic hydrogen.

Embodiments of the processes deposit silicon-containing materials onmany substrates and surfaces. Substrates on which embodiments of theinvention can be useful include, but are not limited to semiconductorwafers, such as crystalline silicon (e.g., Si<100> and Si<111>), siliconon substrate, silicon oxide, silicon germanium, doped or undoped wafersand patterned or non-patterned wafers. Surfaces include wafers, films,layers and materials with dielectric, conductive and barrier propertiesand include polysilicon, silicon on insulators (SOI), strained andunstrained lattices. Some substrate surface may include glass, such asactivated (e.g., Pd) glass substrates. Pretreatment of surfaces includespolishing, etching, activating, reduction, oxidation, hydroxylation,annealing and baking. In one embodiment, wafers are dipped into a 1% HFsolution, dried and baked in a hydrogen atmosphere at 800° C.

Embodiments of the processes may be used to grow silicon-containingfilms with many compositions and properties, including crystalline,amorphous or polysilicon films. Silicon-containing film is the term usedherein to describe a variety of product compositions formed byembodiments of the invention. Some silicon-containing films includecrystalline or pure silicon, silicon germanium, silicon carbon andsilicon germanium carbon. Other silicon-containing films includeepi-SiGe, epi-SiGeC, epi-SiC, poly-SiGe, poly-SiGeC, poly-SiC, α-Si,silicon nitride, silicon oxynitride, silicon oxide and metal silicates(e.g., where metals include titanium, zirconium and hafnium).Silicon-containing films include strained or unstrained layers.

Silicon-containing films may include a germanium concentration withinthe range from about 0 atomic percent to about 95 atomic percent. Inother aspects, a germanium concentration is within the range from about1 atomic percent to about 30 atomic percent. Silicon-containing filmsmay include a carbon concentration within the range from about 0 atomicpercent to about 5 atomic percent. In other aspects, a carbonconcentration is within the range from about 200 ppm to about 2 atomicpercent.

Chlorine and hydrogen incorporation into silicon films has plagued theprior art by the use of lower silanes, lower halosilanes orhexachlorodisilane. Some processes of the invention depositsilicon-containing film that can include impurities, such as hydrogen,halogen and other elements. However, the halogen impurities (e.g., F)occur within the deposited silicon-containing film and are acceptable atless than about 3×10¹⁶ atoms/cm³. Generally, embodiments of theinvention may grow silicon-containing films as thick as a single atomiclayer, about 2.5 Å, and as thick as about 120 μm, preferably with athickness in the range from about 2.5 Å to about 10 μm. Variousembodiments of the invention teach growing films with a thickness in therange from about 10 Å to about 100 Å, from about 100 Å to about 1,000 Å,from about 1,000 Å to about 1 μm, from about 1 μm to about 4 μm, fromabout 4 μm to about 50 μm and from about 50 μm to about 120 μm. In otherembodiments, film thickness is in the range from about 2.5 Å to about120 μm, from about 2.5 Å to about 4 μm and from about 2.5 Å to about 100Å.

The silicon-containing films made by processes of the invention can bedoped. In one embodiment, a selective epitaxy silicon layer is doped Ptype, such as by using diborane to add boron at a concentration in therange from about 10¹⁵ atoms/cm³ to about 10²⁰ atoms/cm³. In anotherembodiment, a polysilicon layer is doped N⁺ type, such as by ionimplanting of phosphorus to a concentration in the range from about 10¹⁹atoms/cm³ to about 10²¹ atoms/cm³. In another embodiment, a selectiveepitaxy silicon layer is doped N⁻ type, such as by diffusion of arsenicor phosphorus to a concentration in the range from about 10¹⁵ atoms/cm³to about 10¹⁹ atoms/cm³.

The silicon-containing films of germanium and/or carbon are produced byvarious processes of the invention and can have consistent, sporadic orgraded elemental concentrations. Graded silicon germanium films aredisclosed in commonly assigned U.S. Ser. No. 09/866,172, published asU.S. Pub. No. 2002-0174826, and issued as U.S. Pat. No. 6,770,134 andcommonly assigned U.S. Ser. No. 10/014,466, published as U.S. Pub. No.2002-0174827, and issued as U.S. Pat. No. 6,905,542, which areincorporated herein by reference in entirety for the purpose ofdescribing methods of depositing graded silicon-containing films. In oneembodiment, silicon germanium sources (e.g., Cl₃SiSiH₂SiCl₂GeH₃) areused to deposit silicon germanium containing films. In anotherembodiment, silicon sources (e.g., Cl₃SiSiH₂SiH₂SiH₃) and alternativegermanium sources (e.g., GeH₄ or Ge₂H₆) are used to deposit silicongermanium containing films. In this embodiment, the ratio of siliconsource and germanium source can be varied in order to provide control ofthe elemental concentrations while growing graded films.

In another embodiment, silicon carbon sources (e.g., Cl₃SiSiH₂SiH₂CH₃)are used to deposit silicon carbon containing films. In anotherembodiment, silicon sources (e.g., Cl₃SiSiH₂SiH₂SiH₃) and alternativecarbon sources (e.g., C₂H₄) are used to deposit silicon carboncontaining films. The ratio of silicon source and carbon source can bevaried in order to provide control of the elemental concentration whilegrowing homogenous or graded films.

Furthermore, in another embodiment, silicon carbon sources (e.g.,Cl₃SiSiH₂SiH₂GeH₃) and alternative germanium sources (e.g., GeH₄ orGe₂H₆) are used to deposit silicon germanium carbon containing films.The amounts of silicon carbon source and germanium source can be variedto provide control of the elemental concentrations while growing gradedfilms. In another embodiment, silicon germanium sources (e.g.,Cl₃SiSiH₂SiH₂GeH₃) and alternative carbon sources (e.g., C₂H₄) are usedto deposit a silicon germanium carbon containing films. The ratio ofsilicon germanium source and carbon source can be varied to providecontrol of the elemental concentrations while growing graded films. Inother embodiments, silicon germanium carbon containing films aredeposited by combining mixtures of silicon sources with silicongermanium sources and/or alternative germanium sources and/or siliconcarbon sources and/or alternative carbon sources. Therefore, any siliconcompound, silicon source, silicon germanium source, silicon carbonsource, alternative silicon source, alternative germanium source andalternative carbon source can be used solely or in combination todeposit silicon-containing films.

Alternative silicon sources may include silanes (e.g., SiH₄) andhalogenated silanes (e.g., H_(4−n)SiX_(n), where X is independently F,Cl, Br or I and n=1-4), for example, ClSiH₃, Cl₂SiH₂, Cl₃SiH and Cl₄Si.Alternative germanium sources may include germanes (e.g., GeH₄, Ge₂H₆,Ge₃H₈ or Ge₄H₁₀) and halogenated germanes (e.g., H_(4−n)GeX_(n), where Xis independently F, Cl, Br or I and n=1-4). Alternative carbon sourcesmay include alkanes (e.g., CH₄, C₂H₆, C₃H₈, C₄H₁₀), halogenated alkanes(e.g., H_(4−n)CX_(n), where X independently F, Cl, Br or I and n=1-4),alkenes (e.g., C₂H₄) and alkynes (e.g., C₂H₂).

Silicon compounds may be used in various deposition processes of theinvention with temperatures in a range from about ambient temperature(e.g., 23° C.) to about 1,200° C. Multiple temperature regions may becontrolled throughout the deposition process, such as the processchamber and a delivery line in fluid communication with a precursorsource and the process chamber. For example, deposition processes may beconducted with a process chamber at a temperature within the range fromabout 100° C. to about 1,000° C. while a delivery line has a temperaturewithin the range from about ambient to about 250° C. In otherembodiments, the process temperature is less than about 700° C. and isoften less than about 500° C. In some embodiments, supplemental reducingagents may be used while depositing a silicon-containing film. In otherembodiments, a silicon-containing film is deposited by pyrolysis of thesilicon compounds.

In processes of the invention, silicon-containing films are grown bychemical vapor deposition (CVD) processes and include ALE and atomiclayer deposition (ALD). Chemical vapor deposition includes the use ofmany techniques, such as plasma-assisted CVD (PA-CVD), thermal-inducedCVD, atomic layer CVD (ALCVD), organometallic or metalorganic CVD (OMCVDor MOCVD), laser-assisted CVD (LA-CVD), ultraviolet CVD (UV-CVD),hot-wire (HWCVD), reduced-pressure CVD (RP-CVD), ultra-high vacuum CVD(UHV-CVD) and others.

In some embodiments of the invention, silicon-containing film may bedeposited by ALD. For example, an ALD process is conducted by sequentialcycles that include: a pulse of a silicon compound, adsorption of thesilicon compound on the substrate or surface, a purge of the reactionchamber, a reduction of the adsorbed silicon compound and a purge of thereaction chamber. Alternatively, when the reduction step includes areductant pulse, such as atomic hydrogen, the cycle includes: a pulse ofa reductant compound, adsorption of the reductant compound on thesubstrate or surface, a purge of the reaction chamber, a pulse of thesilicon compound, reduction of the silicon compound and a purge of thereaction chamber.

The time duration for each silicon compound pulse, the time duration foreach reductant pulse and the duration of the purge gas between pulses ofthe reactants are variable and depend on the volume capacity of adeposition chamber employed, as well as a vacuum system coupled thereto.For example, (1) a lower gas pressure in the chamber will require alonger pulse time; (2) a lower gas flow rate will require a longer timefor chamber pressure to rise and stabilize requiring a longer pulsetime; and (3) a large-volume chamber will take longer to fill, longerfor chamber pressure to stabilize thus requiring a longer pulse time.Similarly, time between each pulse is also variable and depends onvolume capacity of the process chamber as well as the vacuum systemcoupled thereto. In general, the time duration of the silicon compoundpulse or the reductant pulse should be long enough for adsorption of thecompound. In one example, the silicon compound pulse may still be in thechamber when the reductant pulse enters. In general, the duration of thepurge gas should be long enough to prevent the pulses of the siliconcompound and the reductant compound from mixing in the reaction zone.

Generally, a pulse time of about 1.0 second or less for a siliconcompound and a pulse time of about 1.0 second or less for a reductantare typically sufficient to adsorb alternating amounts of reactants on asubstrate or surface. A time of about 1.0 second or less between pulsesof the silicon compound and the reductant is typically sufficient forthe purge gas to prevent the pulses of the silicon compound and thereductant from mixing in the reaction zone. Of course, a longer pulsetime of the reactants may be used to ensure adsorption of the siliconcompound and the reductant and a longer time between pulses of thereactants may be used to ensure removal of the reaction by-products.

The processes of the invention may be carried out in equipment known inthe art of ALE, CVD and ALD. The apparatus brings the sources intocontact with a substrate on which the silicon-containing films aregrown. The processes may operate at a range of pressures from about 1mTorr to about 2,300 Torr depending on specific deposition process andhardware. For example, a silicon-containing film may be deposited by aCVD process with a pressure in the range from about 0.1 Torr to about760 Torr. In another example, a silicon-containing film may be depositedby an ALD process with a pressure in the range from about 760 Torr toabout 1,500 Torr. Hardware that may be used to depositsilicon-containing films includes the Epi CENTURA® system and thePOLYGEN™ system available from Applied Materials, Inc., located in SantaClara, Calif. An ALD apparatus that may be used to depositsilicon-containing films is disclosed in commonly assigned U.S. Ser. No.10/032,284, published as U.S. Pub. No. 2003-0079686, and issued as U.S.Pat. No. 6,916,398, which is incorporated herein by reference inentirety for the purpose of describing the apparatus. Other apparatusesinclude batch, high-temperature furnaces, as known in the art.

Another embodiment of the invention teaches methods to synthesizesilicon compounds comprising SiRX₆, Si₂RX₆, Si₂RX₈, compounds 1-8 andcompounds 9-32, wherein X is independently hydrogen or halogen, R iscarbon, silicon or germanium. Disproportionation reactions ofnon-halogenated, higher silanes are known in the art, such as U.S. Pat.No. 6,027,705, which is incorporated herein by reference in entirety forthe purpose of describing the syntheses of silicon compounds. Silanes,halosilanes, germanes, halogermanes, alkyls and haloalkyls may be usedas starting materials to form silicon compounds. In some embodiments,silicon compounds may be used as starting materials for other siliconcompounds. Starting materials may be made into radical compounds by avariety of methods and include thermal decomposition or plasmaexcitation. Starting material radicals combine to form siliconcompounds. In one example, .SiH₂SiH₃ and .SiCl₂SiCl₃ are respectivelymade from disilane and hexachlorodisilane and are combined to formH₃SiSiH₂SiCl₂SiCl₃. In another example, .SiH₂SiH₂SiH₃ and .GeCl₃ arerespectively made from trisilane and tetrachlorogermane and are combinedto form H₃SiSiH₂SiH₂GeCl₃. In another example, .GeH₃ and.SiCl₂SiCl₂SiCl₃ are respectively made from germane andoctachlorotrisilane and are combined to form H₃GeSiCl₂SiCl₂SiCl₃. Inanother example, .CF₃ and .SiH₂SiH₂SiH₃ are respectively made fromtetrafluoromethane and trisilane and are combined to formF₃CSiH₂SiH₂SiH₃. In another example, .SiH₂SiH₂SiH₃ and .SiCl₂SiCl₃ arerespectively made from trisilane and hexachlorodisilane and are combinedto form H₃SiSiH₂SiH₂SiCl₂SiCl₃. In another example, .SiH₂SiH₂SiH₂SiH₃and .GeCl₃ are respectively made from tetrasilane and tetrachlorogermaneand are combined to form H₃SiSiH₂SiH₂SiH₂GeCl₃. In another example,.GeH₃ and .SiCl₂SiCl₂SiCl₂SiCl₃ are respectively made from germane anddecachlorotetrasilane and are combined to form H₃GeSiCl₂SiCl₂SiCl₂SiCl₃.In another example, .CF₃ and .SiH₂SiH₂SiH₂SiH₃ are respectively madefrom tetrafluoromethane and tetrasilane and are combined to formF₃CSiH₂SiH₂SiH₂SiH₃.

Theoretical Experiments 1-17 Including Silicon Compounds SiRX₆

Example 1 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 30 sccm ofCl₃SiSiH₃, was delivered to the chamber at 10 Torr and 750° C. Thesubstrate was maintained at 750° C. Deposition was carried out for 3minutes to form a 400 Å epitaxial layer on the silicon surface, but noepitaxial growth occurred on the silicon dioxide surface.

Example 2 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 50 sccm ofCl₃SiSiH₃, was added to the chamber at 100 Torr and 650° C. Thesubstrate was maintained at 650° C. Deposition was carried out for 4minutes to form a 1,600 Å epitaxial layer.

Example 3 Polysilicon by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (POLYGEN™ chamber) and subjected to a hydrogenpurge for 2 minutes. A flow of carrier gas, hydrogen, was directedtowards the substrate and the source compounds were added to the carrierflow. The silicon compound, 100 sccm of HF₂SiSiClH₂, was added to thechamber at 80 Torr and 550° C. The substrate was maintained at 550° C.Deposition was carried out for 3 minutes to form a 1,200 Å layer.

Example 4 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber(Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. Aflow of carrier gas, hydrogen, was directed towards the substrate andthe source compounds were added to the carrier flow. The siliconcompound, 200 sccm of HCl₂SiSiH₃, was added to the chamber at 200 Torrand 40° C. The substrate was maintained at 40° C. Deposition was carriedout for 3 minutes to form a 200 Å layer.

Example 5 Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 1 minute. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm HCl₂SiGeH₃, was added tothe chamber at 100 Torr and 650° C. The substrate was maintained at 650°C. Deposition was carried out for 5 minutes to form a 600 Å epitaxiallayer.

Example 6 Silicon Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂CSiH₃, was addedto the chamber at 100 Torr and 500° C. The substrate was maintained at500° C. Deposition was carried out for 15 minutes to form a 1,400 Åepitaxial layer.

Example 7 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiGeH₃, was addedto the chamber at 100 Torr and 550° C. The silicon compound, H₃CSiH₃,was also added to the chamber at 2 sccm. The substrate was maintained at550° C. Deposition was carried out for 10 minutes to form a 2,100 Åepitaxial layer.

Example 8 Doped Silicon CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₃, was addedto the chamber at 100 Torr and 750° C. The dopant compound, 1 sccm of1000 ppm B₂H₆ in H₂, was also added to the chamber. The substrate wasmaintained at 750° C. Deposition was carried out for 3 minutes to form a600 Å epitaxial doped layer.

Example 9 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₃, was addedto the chamber at 10 Torr and 650° C. A decreasing flow from 225 sccmdown to 5 sccm of the silicon compound, HCl₂SiGeH₃, was also added tothe chamber during the deposition step. The flow rate was changednon-linearly in respect to time to produce a linearly graded finalgermanium content in the deposited film. The substrate was maintained at550° C. Deposition was carried out for 5 minutes to form a 1,200 Åepitaxial layer.

Example 10 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of HCl₂SiCH₃, was addedto the chamber at 10 Torr and 650° C. Also, 10 sccm of 5% H₃CSiH₃ wasadded to the chamber. A decreasing flow from 350 sccm down to 5 sccm ofthe silicon compound, HCl₂SiGeH₃, was also added to the chamber duringthe deposition step. The flow rate was changed non-linearly to produce alinearly graded final germanium content in the deposited film. Thesubstrate was maintained at 550° C. Deposition was carried out for 5minutes to form a 1,300 Å epitaxial layer.

Example 11 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 1. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₃, was addedto the chamber at 10 Torr and 600° C. A 5 sccm flow of hydrogen chloridewas also delivered to the chamber. The substrate was maintained at 600°C. Deposition was carried out for 8 minutes to form a 500 Å epitaxiallayer on the silicon surface, but no epitaxial growth occurred on thesilicon dioxide surface.

Example 12 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. The H-atoms are generatedvia a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₃ (0.8 s), purge(1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included:HCl₂SiGeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). Agraded film is grown by running a sequence of cycles such as: 10A, 1B,5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintained at 300° C.Deposition was carried out for 40 minutes to form a 2,200 Å layer.

Example 13 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. ALD cycle included:HCl₂SiCH₃ (0.8 s), purge (1.0 s), HCl₂SiGeH₃ (0.8 s), purge (1.0 s). Afilm is grown by running cycles for a desired film thickness. Thesubstrate was maintained at 500° C. Deposition was carried out for 40minutes to form a 2,000 Å layer.

Example 14 Synthesis of H₃SiSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Silane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiSiCl₃.

Example 15 Synthesis of H₃SiGeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Silane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiGeCl₃.

Example 16 Synthesis of H₃GeSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃GeSiCl₃.

Example 17 Synthesis of F₃CSiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at arate of 15 L/min. Tetrachlorosilane was supplied to reactor 1 at a rateof 15 L/min. The outlet gas of reactor 2 was analyzed to find that theyields of silane compounds and silicon compounds including F₃CSiCl₃.

Theoretical Experiments 18-34 Including Silicon Compounds Si₂RX₈

Example 18 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 30 sccm ofCl₃SiSiH₂SiH₃, was delivered to the chamber at 10 Torr and 750° C. Thesubstrate was maintained at 750° C. Deposition was carried out for 3minutes to form a 400 Å epitaxial layer on the silicon surface, but noepitaxial growth occurred on the silicon dioxide surface.

Example 19 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 50 sccm ofCl₃SiSiH₂SiH₃, was added to the chamber at 100 Torr and 650° C. Thesubstrate was maintained at 650° C. Deposition was carried out for 4minutes to form a 1,600 Å epitaxial layer.

Example 20 Polysilicon by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (POLYGEN™ chamber) and subjected to a hydrogenpurge for 2 minutes. A flow of carrier gas, hydrogen, was directedtowards the substrate and the source compounds were added to the carrierflow. The silicon compound, 100 sccm of HF₂SiSiH₂SiClH₂, was added tothe chamber at 80 Torr and 550° C. The substrate was maintained at 550°C. Deposition was carried out for 3 minutes to form a 1,200 Å layer.

Example 21 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber(Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. Aflow of carrier gas, hydrogen, was directed towards the substrate andthe source compounds were added to the carrier flow. The siliconcompound, 200 sccm of HCl₂SiSiH₂SiH₃, was added to the chamber at 200Torr and 40° C. The substrate was maintained at 40° C. Deposition wascarried out for 3 minutes to form a 200 Å layer.

Example 22 Silicon Germanium by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 1 minute. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm HCl₂SiSiH₂GeH₃, wasadded to the chamber at 100 Torr and 650° C. The substrate wasmaintained at 650° C. Deposition was carried out for 5 minutes to form a600 Å epitaxial layer.

Example 23 Silicon Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂CSiH₂SiH₃, wasadded to the chamber at 100 Torr and 500° C. The substrate wasmaintained at 500° C. Deposition was carried out for 15 minutes to forma 1,400 Å epitaxial layer.

Example 24 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂GeH₃, wasadded to the chamber at 100 Torr and 550° C. The silicon compound,H₃CSiH₂SiH₃, was also added to the chamber at 2 sccm. The substrate wasmaintained at 550° C. Deposition was carried out for 10 minutes to forma 2,100 Å epitaxial layer.

Example 25 Doped Silicon CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₂SiH₃, wasadded to the chamber at 100 Torr and 750° C. The dopant compound, 1 sccmof 1000 ppm B₂H₆ in H₂, was also added to the chamber. The substrate wasmaintained at 750° C. Deposition was carried out for 3 minutes to form a600 Å epitaxial doped layer.

Example 26 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₂SiH₃, wasadded to the chamber at 10 Torr and 650° C. A decreasing flow from 225sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, was alsoadded to the chamber during the deposition step. The flow rate waschanged non-linearly in respect to time to produce a linearly gradedfinal germanium content in the deposited film. The substrate wasmaintained at 550° C. Deposition was carried out for 5 minutes to form a1,200 Å epitaxial layer.

Example 27 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of HCl₂SiSiH₂CH₃, wasadded to the chamber at 10 Torr and 650° C. Also, 10 sccm of 5%H₃CSiH₂SiH₃ was added to the chamber. A decreasing flow from 350 sccmdown to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, was also addedto the chamber during the deposition step. The flow rate was changednon-linearly to produce a linearly graded final germanium content in thedeposited film. The substrate was maintained at 550° C. Deposition wascarried out for 5 minutes to form a 1,300 Å epitaxial layer.

Example 28 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 18. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₃, wasadded to the chamber at 10 Torr and 600° C. A 5 sccm flow of hydrogenchloride was also delivered to the chamber. The substrate was maintainedat 600° C. Deposition was carried out for 8 minutes to form a 500 Åepitaxial layer on the silicon surface, but no epitaxial growth occurredon the silicon dioxide surface.

Example 29 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. The H-atoms are generatedvia a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₂SiH₃ (0.8 s),purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included:HCl₂SiSiH₂GeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). Agraded film is grown by running a sequence of cycles such as: 10A, 1B,5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintained at 300° C.Deposition was carried out for 40 minutes to form a 2,200 Å layer.

Example 30 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 19. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. ALD cycle included:HCl₂SiSiH₂CH₃ (0.8 s), purge (1.0 s), HCl₂SiSiH₂GeH₃ (0.8 s), purge (1.0s). A film is grown by running cycles for a desired film thickness. Thesubstrate was maintained at 500° C. Deposition was carried out for 40minutes to form a 2,000 Å layer.

Example 31 Synthesis of H₃SiSiH₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorosilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiSiH₂SiCl₃.

Example 32 Synthesis of H₃SiSiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiSiH₂GeCl₃.

Example 33 Synthesis of H₃GeSiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃GeSiCl₂SiCl₃.

Example 34 Synthesis of F₃CSiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at arate of 15 L/min. Disilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including F₃CSiH₂SiH₃.

Theoretical Experiments 35-56 Including Silicon Compounds from Compounds1-32

Example 35 Monocrystalline Silicon by Selective CVD

A substrate, Si<100>, was employed to investigate selective,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 30 sccm ofCl₃SiSiH₂SiH₂SiH₃, was delivered to the chamber at 10 Torr and 750° C.The substrate was maintained at 750° C. Deposition was carried out for 3minutes to form a 400 Å epitaxial layer on the silicon surface, but noepitaxial growth occurred on the silicon dioxide surface.

Example 36 Monocrystalline Silicon by Blanket CVD

A substrate, Si<100>, was employed to investigate blanket,monocrystalline film growth by CVD. A silicon oxide feature existed onthe surface of the wafer. The wafer was prepared by subjecting to a 0.5%HF dip for 30 seconds followed by baking at 750° C. for 60 seconds. Thewafer was loaded into the deposition chamber (Epi CENTURA® chamber) andsubjected to a hydrogen purge for 2 minutes. A flow of carrier gas,hydrogen, was directed towards the substrate and the source compoundswere added to the carrier flow. The silicon compound, 50 sccm ofCl₃SiSiH₂SiH₂SiH₃, was added to the chamber at 100 Torr and 650° C. Thesubstrate was maintained at 650° C. Deposition was carried out for 4minutes to form a 1,600 Å epitaxial layer.

Example 37 Polysilicon by CVD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber (POLYGEN™ chamber) and subjected to a hydrogenpurge for 2 minutes. A flow of carrier gas, hydrogen, was directedtowards the substrate and the source compounds were added to the carrierflow. The silicon compound, 100 sccm of HF₂SiSiH₂SiH₂SiH₂SiClH₂, wasadded to the chamber at 80 Torr and 550° C. The substrate was maintainedat 550° C. Deposition was carried out for 3 minutes to form a 1,200 Ålayer.

Example 38 Amorphous Silicon by CVD

A silicon dioxide layered wafer was loaded into the deposition chamber(Epi CENTURA® chamber) and subjected to a hydrogen purge for 1 minute. Aflow of carrier gas, hydrogen, was directed towards the substrate andthe source compounds were added to the carrier flow. The siliconcompound, 200 sccm of HCl₂SiSiH₂SiH₂SiH₂SiH₃, was added to the chamberat 200 Torr and 40° C. The substrate was maintained at 40° C. Depositionwas carried out for 3 minutes to form a 200 Å layer.

Example 39 Silicon Germanium by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 1 minute. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm HCl₂SiSiH₂SiH₂SiH₂GeH₃,was added to the chamber at 100 Torr and 650° C. The substrate wasmaintained at 650° C. Deposition was carried out for 5 minutes to form a600 Å epitaxial layer.

Example 40 Silicon Carbon by CVD

The substrate was prepared as in Example 2. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm ofHCl₂CSiH₂SiH₂SiH₂SiH₃, was added to the chamber at 100 Torr and 500° C.The substrate was maintained at 500° C. Deposition was carried out for15 minutes to form a 1,400 Å epitaxial layer.

Example 41 Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₂GeH₃,was added to the chamber at 100 Torr and 550° C. The silicon compound,H₃CSiH₂SiH₂SiH₃, was also added to the chamber at 2 sccm. The substratewas maintained at 550° C. Deposition was carried out for 10 minutes toform a 2,100 Å epitaxial layer.

Example 42 Doped Silicon CVD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of Cl₃SiSiH₂SiH₂SiH₃,was added to the chamber at 100 Torr and 750° C. The dopant compound, 1sccm of 1000 ppm B₂H₆ in H₂, was also added to the chamber. Thesubstrate was maintained at 750° C. Deposition was carried out for 3minutes to form a 600 Å epitaxial doped layer.

Example 43 Graded Silicon Germanium by CVD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 50 sccm of HCl₂SiSiH₂SiH₂SiH₃,was added to the chamber at 10 Torr and 650° C. A decreasing flow from225 sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂GeH₃, wasalso added to the chamber during the deposition step. The flow rate waschanged non-linearly in respect to time to produce a linearly gradedfinal germanium content in the deposited film. The substrate wasmaintained at 550° C. Deposition was carried out for 5 minutes to form a1,200 Å epitaxial layer.

Example 44 Graded Silicon Germanium Carbon by CVD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 100 sccm of HCl₂SiSiH₂SiH₂GeH₃,was added to the chamber at 10 Torr and 650° C. Also, 10 sccm of 5%H₃CSiH₂SiH₂SiH₃ was added to the chamber. A decreasing flow from 350sccm down to 5 sccm of the silicon compound, HCl₂SiSiH₂SiH₂GeH₃, wasalso added to the chamber during the deposition step. The flow rate waschanged non-linearly to produce a linearly graded final germaniumcontent in the deposited film. The substrate was maintained at 550° C.Deposition was carried out for 5 minutes to form a 1,300 Å epitaxiallayer.

Example 45 Monocrystalline Selective Silicon by CVD with Use of HCl

The substrate was prepared as in Example 35. The wafer was loaded intothe deposition chamber (Epi CENTURA® chamber) and subjected to ahydrogen purge for 2 minutes. A flow of carrier gas, hydrogen, wasdirected towards the substrate and the source compounds were added tothe carrier flow. The silicon compound, 10 sccm of HCl₂SiSiH₂SiH₂SiH₃,was added to the chamber at 10 Torr and 600° C. A 5 sccm flow ofhydrogen chloride was also delivered to the chamber. The substrate wasmaintained at 600° C. Deposition was carried out for 8 minutes to form a500 Å epitaxial layer on the silicon surface, but no epitaxial growthoccurred on the silicon dioxide surface.

Example 46 Graded Silicon Germanium by ALD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. The H-atoms are generatedvia a tungsten hot-wire. ALD cycle A included: HCl₂SiSiH₂SiH₂SiH₃ (0.8s), purge (1.0 s), H-atoms (1.2 s), purge (1.0 s). ALD cycle B included:HCl₂SiSiH₂SiH₂SiH₂GeH₃ (0.8 s), purge (1.0 s), H-atoms (1.2 s), purge(1.0 s). A graded film is grown by running a sequence of cycles such as:10A, 1B, 5A, 1B, 1A, 1B, 1A, 5B, 1A, 10B. The substrate was maintainedat 300° C. Deposition was carried out for 40 minutes to form a 2,200 Ålayer.

Example 47 Graded Silicon Germanium Carbon by ALD

The substrate was prepared as in Example 36. The wafer was loaded intothe deposition chamber and subjected to a hydrogen purge for 10 minutes.A flow of carrier gas, argon, was directed towards the substrate and thesource compounds were pulsed into this flow. ALD cycle included:HCl₂SiSiH₂SiH₂GeH₃ (0.8 s), purge (1.0 s), HCl₂SiSiH₂SiH₂CH₃ (0.8 s),purge (1.0 s). A film is grown by running cycles for a desired filmthickness. The substrate was maintained at 500° C. Deposition wascarried out for 40 minutes to form a 2,000 Å layer.

Example 48 Synthesis of H₃SiSiH₂SiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Disilane was supplied to reactor 1 at a rate of 15L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiSiH₂SiCl₂SiCl₃.

Example 49 Synthesis of H₃SiSiH₂SiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Trisilane was supplied to reactor 1 at a rate of 15L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including H₃SiSiH₂SiH₂GeCl₃.

Example 50 Synthesis of Cl₃SiSiCl₂SiCl₂GeH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Germane was supplied to reactor 1 at a rate of 15L/min. Octachlorotrisilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including Cl₃SiSiCl₂SiCl₂GeH₃.

Example 51 Synthesis of F₃CSiH₂SiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at arate of 15 L/min. Trisilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including F₃CSiH₂SiH₂SiH₃.

Example 52 Synthesis of H₃SiSiH₂SiH₂SiCl₂SiCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Trisilane was supplied to reactor 1 at a rate of 15L/min. Hexachlorodisilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds includingH₃SiSiH₂SiH₂SiCl₂SiCl₃.

Example 53 Synthesis of H₃SiSiH₂SiH₂SiH₂GeCl₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Tetrasilane was supplied to reactor 1 at a rate of15 L/min. Tetrachlorogermane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds includingH₃SiSiH₂SiH₂SiH₂GeCl₃.

Example 54 Synthesis of Cl₃SiSiCl₂SiCl₂SiCl₂GeH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Decachlorotetrasilane was supplied to reactor 1 ata rate of 15 L/min. Germane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds includingCl₃SiSiCl₂SiCl₂SiCl₂GeH₃.

Example 55 Synthesis of F₃CSiH₂SiH₂SiH₂SiH₃

A 2.5 L SUS (reactor 1) and a 5 L SUS (reactor 2) were connected in thedirect series, the inside temperature of reactor 1 was set to 450° C.and the inside temperature of reactor 2 was set to 350° C. The pressurewas set to 0.13 MPa. Tetrafluoromethane was supplied to reactor 1 at arate of 15 L/min. Tetrasilane was supplied to reactor 1 at a rate of 15L/min. The outlet gas of reactor 2 was analyzed to find that the yieldsof silane compounds and silicon compounds including F₃CSiH₂SiH₂SiH₂SiH₃.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow

1. A method for depositing a silicon-containing film, comprising:delivering a silicon compound to a surface or a substrate; and reactingthe silicon compound to grow the silicon-containing film, wherein thesilicon compound comprises one or more compounds having a formulaselected from the group consisting of Si₄X₈, Si₄X₁₀, Si₅X₁₀, and Si₅X₁₂,where X is independently a hydrogen or halogen.
 2. The method of claim1, wherein the silicon compound comprises Si₅X₁₂.
 3. The method of claim1, wherein X is a hydrogen.
 4. The method of claim 1, wherein X is ahalogen.
 5. The method of claim 1, wherein the silicon-containing filmis doped.
 6. The method of claim 1, wherein the silicon-containing filmhas a thickness in a range from about 2.5 Å to about 120 μm.
 7. Themethod of claim 6, wherein the thickness is about 2.5 Å to about 4 μm.8. The method of claim 6, wherein the thickness is about 2.5 Å to about100 Å.
 9. A method for depositing a silicon-containing film by atomiclayer epitaxy, comprising: heating a substrate or a surface to atemperature, and reacting the silicon compound to deposit thesilicon-containing film, wherein the silicon compound comprises one ormore compounds having a formula selected from the group consisting ofSi₄X₈, Si₄X₁₀, Si₅X₁₀, and Si₅X₁₂, where X is independently a hydrogenor halogen.
 10. The method of claim 9, wherein the silicon compoundcomprises Si₅X₁₂.
 11. The method of claim 9, wherein X is a hydrogen.12. The method of claim 9, wherein X is a halogen.
 13. The method ofclaim 9, wherein the temperature is in a range from about 400° C. toabout 800° C.
 14. The method of claim 9, wherein the surface or thesubstrate is heated to a temperature less than about 500° C.
 15. Amethod for depositing a silicon-containing film, comprising: deliveringa silicon compound to a surface of a substrate; and reacting the siliconcompound to grow the silicon-containing film, wherein the siliconcompound comprises a compound having the formula:

wherein X₁-X₁₀ are independently hydrogen or halogen, and R is carbon,silicon, or germanium.
 16. The method of claim 15, wherein X₁-X₁₀ arehydrogens.
 17. The method of claim 15, wherein R is silicon.
 18. Amethod for depositing a silicon-containing film, comprising: deliveringa silicon compound to a surface of a substrate; and reacting the siliconcompound to grow the silicon-containing film, wherein the siliconcompound comprises a compound having the formula:

wherein X₁-X₁₀ are independently hydrogen or halogen, and R is carbon,silicon, or germanium.
 19. The method of claim 18, wherein X₁-X₁₀ arehydrogens.
 20. The method of claim 18, wherein R is silicon.
 21. Amethod for depositing a silicon-containing film, comprising: deliveringa silicon compound to a surface of a substrate; and reacting the siliconcompound to grow the silicon-containing film, wherein the siliconcompound comprises a compound having the formula:

wherein X₁-X₁₂ are independently hydrogen or halogen, and R is carbon,silicon, or germanium.
 22. The method of claim 21, wherein X₁-X₁₂ arehydrogens.
 23. The method of claim 21, wherein R is silicon.